CN114302867B

CN114302867B - Covering component

Info

Publication number: CN114302867B
Application number: CN202080060620.8A
Authority: CN
Inventors: 藤井健辅
Original assignee: Asahi Glass Co Ltd
Current assignee: AGC Inc
Priority date: 2019-08-26
Filing date: 2020-08-19
Publication date: 2023-10-03
Anticipated expiration: 2040-08-19
Also published as: US20220177365A1; US11787734B2; EP4023618B1; EP4023618A4; WO2021039552A1; EP4023618A1; TWI845748B; JPWO2021039552A1; CN114302867A; JP7435612B2; TW202120307A

Abstract

The present invention relates to a cover member comprising: a transparent substrate having a first main surface and a second main surface; an anti-fouling layer formed on at least a portion of the first major surface; a printed layer formed on at least a portion of the second main surface; and an adhesive member adhered to the surface on the side of the stain-proofing layer, wherein a predetermined region in the second main surface is defined as an adhesive member contact portion projection region, and at least a part of a region from the boundary of the region to a region located 1000 [ mu ] m inward from the boundary of the region, that is, a region near the boundary, is provided with a print layer, and at least a part of a region located 500 [ mu ] m inward from the boundary of the adhesive member contact portion projection region, that is, an inner region, is not provided with a print layer.

Description

Covering component

Technical Field

The present invention relates to a cover member.

Background

In recent years, there have been increasing cases in which a protective plate for improving the protection and the appearance of a display surface of a display is used for a mobile device such as a tablet PC (Personal Computer personal computer) or a smart phone, or for a display device such as a liquid crystal television or a touch panel (hereinafter, these are sometimes collectively referred to as a display device or the like).

In these protective plates (hereinafter, also referred to as cover glass), an antifouling layer is often formed to suppress adhesion of dirt due to fingerprints, sebum, sweat, and the like. In addition, in order to improve the abrasion resistance of the antifouling layer, an adhesion layer may be formed between the antifouling layer and the protective plate. In addition, in order to improve the visibility of the display, an antireflection property and an antiglare property may be provided to the adhesion layer.

Depending on the application of the protection plate, the surface-mounted component may be required. For example, in a vehicle-mounted display such as car navigation, a button-like or dial-like member for adjusting the volume of an air conditioner or a radio is sometimes mounted on a surface of a cover glass on a Center Information Display (CID) on a side where a finger of a person is in contact when in use.

Patent document 1 discloses a method for securing adhesion between such a member and the outermost surface of a cover glass.

As disclosed in patent document 1, a printed layer may be provided on the cover glass from the viewpoint of aesthetic appearance and the like.

Patent document 1: japanese patent laid-open publication No. 2018-48061

However, the inventors have newly found that, in the cover glass on which a dial-like or button-like member (hereinafter, also referred to as an "adhesive member") is mounted, when a printed layer is present on the rear surface side corresponding to the position where the member is mounted, the following problems occur. That is, when a person operates the adhesive member, a load such as pressing the cover glass is generated. In addition, when a person or an object touches or collides with the adhesive member, a strong force may be applied to the corner of the adhesive member to locally bend the cover glass. It has been found that when such locally strong load is applied a plurality of times, locally strong tensile stress is generated in the printed layer on the back surface, and a strong shear force is applied between the cover glass and the printed layer, and as a result, cracks and peeling are likely to occur in the printed layer.

Disclosure of Invention

The present invention has been made in view of the above circumstances, and an object thereof is to provide a cover member in which the risk of cracking and peeling of a printed layer is reduced even when used for a long period of time.

The first cover member according to the present invention for solving the above-described problems is a cover member comprising a transparent substrate, an anti-fouling layer, a print layer, and an adhesive member, wherein the transparent substrate has a first main surface and a second main surface, the anti-fouling layer is formed on at least a part of the first main surface, the print layer is formed on at least a part of the second main surface, the adhesive member is adhered to one side of the anti-fouling layer, the adhesive member is adhered to the transparent substrate or the anti-fouling layer, a region obtained by projecting a region of the adhesive member substantially in contact with the transparent substrate or the second main surface so as to be parallel to the thickness direction of the transparent substrate is an adhesive member contact projection region, a region from a boundary of the adhesive member contact projection region to a region located 1000 [ mu ] m inside the boundary of the region is a boundary vicinity region, and when the region located 500 [ mu ] m inside the boundary of the adhesive member contact projection region is an inside region, at least a part of the boundary vicinity region is provided with the print layer, and at least a part of the inside region is not provided with the print layer.

In one embodiment of the cover member of the present invention, the first main surface of the transparent substrate may further include a region where the stain-proofing layer is substantially absent in a region where the adhesive member is substantially in contact with the transparent substrate or the stain-proofing layer, and when a region where the stain-proofing layer is substantially absent is projected onto the second main surface so as to be parallel to the thickness direction of the transparent substrate is defined as a stain-proofing layer absent portion projected region, at least a part of the stain-proofing layer absent portion projected region may be included in the inner region, and a part of the stain-proofing layer absent portion projected region included in the inner region may not include the print layer.

In one embodiment of the covering member of the present invention, the entire projection area of the antifouling layer non-existing portion may be included in the inner area.

In one embodiment of the cover member of the present invention, the adhesive member may be formed in a ring shape, and a portion continuous in the circumferential direction of the ring and not provided with a print layer may be provided in at least a part of the inner region.

In one embodiment of the cover member of the present invention, the print layer may be formed in a band shape along an end portion of the transparent substrate, the adhesive member contact portion projection region may include one end portion and the other end portion in the width direction of the print layer, and the adhesive member contact portion projection region may include: a portion having no print layer is continuously formed between one end portion and the other end portion in the width direction of the print layer.

In one embodiment of the cover member of the present invention, when a region from the outer peripheral end to a portion of the second main surface located 50 μm inward from the outer peripheral end is defined as a region near the outer peripheral end, a portion of the inner region may be included in the region near the outer peripheral end, and a portion of the inner region included in the region near the outer peripheral end may be provided with no print layer.

The second cover member according to the present invention for solving the above-described problems is a cover member comprising a transparent substrate, an antifouling layer, and a print layer, wherein the transparent substrate has a first main surface and a second main surface, the antifouling layer is formed on at least a part of the first main surface, the print layer is formed on at least a part of the second main surface, the first main surface has a region where the antifouling layer is substantially absent, the region where the antifouling layer is substantially absent is projected onto the second main surface so as to be parallel to the thickness direction of the transparent substrate, the region where the antifouling layer is absent is a projected region, and when the region 500 μm or more inside the boundary of the region in the projected region where the antifouling layer is absent is an inside region, at least a part of the inside region is not provided with the print layer.

In one embodiment of the covering member of the present invention, the projected area of the portion where the antifouling layer does not exist may be formed in a ring shape.

In one embodiment of the cover member of the present invention, when the region from the outer peripheral end to the portion 50 μm inward from the outer peripheral end of the second main surface is defined as the outer peripheral end-near region, a part of the antifouling layer non-existing portion projection region may be included in the outer peripheral end-near region, and a part of the antifouling layer non-existing portion projection region included in the outer peripheral end-near region may not include the printing layer.

In one embodiment of the cover member of the present invention, the printed layer may not be provided on the entire projection area where the stain-proofing layer does not exist.

In one embodiment of the cover member of the present invention, the print layer may be formed in a band shape along an end portion of the transparent substrate, and the antifouling layer non-existing portion projection area may include one end portion and the other end portion in the width direction of the print layer, and the antifouling layer non-existing portion projection area may include a portion not including the print layer, which is continuously formed between the one end portion and the other end portion in the width direction of the print layer.

In one embodiment of the cover member of the present invention, the transparent substrate may be a glass substrate.

In one embodiment of the cover member of the present invention, the glass substrate may be a chemically strengthened glass substrate.

In one embodiment of the cover member of the present invention, an adhesion layer may be further provided between the first main surface of the transparent substrate and the stain-proofing layer.

The cover member of the present invention reduces the risk of cracking and peeling in the printed layer even when used for a long period of time.

Drawings

Fig. 1 is a top view of a cover member in one embodiment of the invention.

Fig. 2 is a cross-sectional view taken along line A-A of fig. 1.

Fig. 3 is a plan view of the cover member according to the first embodiment.

Fig. 4 is a sectional view taken along line B-B of fig. 3.

Fig. 5 is an enlarged view of the periphery of the adhesive member of the cover member of the first embodiment as viewed from the printed layer side.

Fig. 6 is a plan view of a cover member according to a second embodiment.

Fig. 7 is a sectional view taken along line C-C of fig. 6.

Fig. 8 is an enlarged view of the periphery of the adhesive member of the cover member of the second embodiment as viewed from the printed layer side.

Fig. 9 is a plan view of a cover member according to a third embodiment.

Fig. 10 is an enlarged view of the periphery of the adhesive member of the cover member of the third embodiment as viewed from the printed layer side.

Fig. 11 is a plan view of a cover member according to a fourth embodiment.

Fig. 12 is a sectional view taken along line D-D of fig. 11.

Fig. 13 is an enlarged view of the periphery of the adhesive member of the cover member of the fourth embodiment as viewed from the printed layer side.

Fig. 14 is a plan view of a cover member according to a fifth embodiment.

Fig. 15 is a sectional view taken along line E-E of fig. 14.

Fig. 16 is an enlarged view of the periphery of the adhesive member of the cover member of the fifth embodiment as viewed from the printed layer side.

Fig. 17 is a plan view of a cover member according to a sixth embodiment.

Fig. 18 is a sectional view taken along line F-F of fig. 17.

Fig. 19 is an enlarged view of the periphery of the adhesive member of the cover member of the sixth embodiment as viewed from the printed layer side.

Fig. 20 is a schematic view of the cover member of example 1 as viewed from the printed layer side.

Fig. 21 is a schematic view of the cover member of example 2 viewed from the printing layer side.

Fig. 22 is a schematic view of the cover member of example 3 as viewed from the printed layer side.

Fig. 23 is a schematic view of the cover member of example 4 viewed from the printed layer side.

Detailed Description

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the embodiments described below. In order to clearly illustrate the present invention, the embodiments described in the drawings are schematically illustrated, and do not necessarily represent actual dimensions or scales accurately.

< first embodiment >, first embodiment

[ cover Member ]

Fig. 1 shows a top view of a cover member 10 according to a first embodiment of the present invention. A cross-sectional view along line A-A of fig. 1 is shown in fig. 2.

The cover member 10 of the present embodiment includes a transparent substrate 1, an antifouling layer 2, a print layer 3, and an adhesive member 4.

The transparent substrate 1 has a first main surface 1A and a second main surface 1B. The stain-proofing layer 2 is formed on at least a part of the first main surface 1A of the transparent substrate 1. The printed layer 3 is formed on at least a part of the second main surface 1B of the transparent substrate 1. The adhesive member is adhered to the surface of the stain-proofing layer 2 side.

These details will be described below.

[ transparent substrate ]

The transparent substrate 1 is not particularly limited as long as it is a substrate made of a transparent material, and for example, a substrate made of glass, resin, or a composite material or a laminate material obtained by combining these materials is preferably used.

Examples of the resin used as the material of the transparent substrate include acrylic resins such as polymethyl methacrylate, aromatic polycarbonate resins such as bisphenol a carbonate, and aromatic polyester resins such as polyethylene terephthalate.

Examples of the glass used as the material of the transparent substrate include general glass mainly composed of silica, for example, glass such as soda lime silicate glass, aluminosilicate glass, borosilicate glass, alkali-free glass, and quartz glass.

When a glass substrate is used as the transparent substrate, the glass preferably has a composition that can be molded and strengthened by a chemical strengthening treatment, and preferably contains sodium.

The composition of the glass is not particularly limited, and glass having various compositions can be used. For example, aluminosilicate glass having the following composition in mol% based on the oxide can be used. (i) Contains 50 to 80 percent of SiO ₂ 2 to 25 percent of Al ₂ O ₃ 0 to 20 percent of Li ₂ O, na 0-18% ₂ O、0～10% of K ₂ O, mgO 0-15%, caO 0-5%, Y0-5% ₂ O ₃ ZrO 0-5% ₂ Is a glass of (a). (ii) Contains 50 to 74 percent of SiO ₂ 1 to 10 percent of Al ₂ O ₃ 6 to 14 percent of Na ₂ O, 3-11% of K ₂ O, 2-15% MgO, 0-6% CaO and 0-5% ZrO ₂ And SiO ₂ Al and Al ₂ O ₃ The total content of Na is less than 75 percent ₂ O and K ₂ Glass having a total O content of 12 to 25% and a total MgO and CaO content of 7 to 15%. (iii) Contains 68-80% of SiO ₂ 4-10% of Al ₂ O ₃ 5 to 15 percent of Na ₂ O, 0-1% of K ₂ O, 4-15% MgO and 0-1% ZrO ₂ Is a glass of (a). (iv) Contains 67-75% of SiO ₂ 0 to 4 percent of Al ₂ O ₃ Na of 7-15% ₂ O, 1-9% of K ₂ O, 6 to 14 percent of MgO and 0 to 1.5 percent of ZrO ₂ And SiO ₂ Al and Al ₂ O ₃ The total content of (C) is 71-75%, na ₂ O and K ₂ The total content of O is 12 to 20%, and when CaO is contained, the content is less than 1%.

The transparent substrate is preferably a glass substrate from the viewpoints of aesthetic properties and strength.

The method for producing the glass substrate is not particularly limited. For example, a glass raw material may be charged into a melting furnace so as to have a desired composition, heated and melted at 1500 to 1600 ℃ and clarified, and then supplied to a forming apparatus, and the molten glass may be formed into a plate shape and gradually cooled to produce a glass substrate. The method for forming the glass substrate is not limited to this method, and for example, a downdraw method such as overflow downdraw method, slot downdraw method, and redraw method, a float method, a roll-out method, a press method, and the like may be used.

In the case of using a glass substrate as the transparent substrate, the glass substrate is preferably a glass substrate subjected to a strengthening treatment. In particular, the glass substrate is preferably a chemically strengthened glass substrate subjected to a chemical strengthening treatment.

The chemical strengthening treatment method is not particularly limited, and the main surface of the glass substrate is ion-exchanged to form a surface layer (compressive stress layer) in which compressive stress remains. Specifically, alkali metal ions having a smaller ion radius contained in the glass near the main surface of the substrate are replaced with alkali metal ions having a larger ion radius at a temperature equal to or lower than the glass transition point. Thus, compressive stress remains on the main surface of the glass substrate, and the strength of the glass substrate is improved. Here, the alkali metal ions having a small ionic radius are, for example, li ions and Na ions. The alkali metal ion having a larger ion radius is, for example, na ion or K ion relative to Li ion, and K ion relative to Na ion.

The glass substrate as the transparent substrate preferably satisfies the following conditions. Such conditions can be satisfied by performing the chemical strengthening treatment described above.

From the viewpoint of practical strength, the surface compressive stress (hereinafter referred to as cs.) of the glass substrate is preferably 400MPa or more, more preferably 700MPa or more. In order to eliminate the risk that the glass substrate cannot withstand the compressive stress of the glass substrate itself and is naturally damaged, CS of the glass substrate is preferably 1200MPa or less, more preferably 900MPa or less, and still more preferably 850MPa or less.

In particular, when the cover member according to the present embodiment is used as a cover member (cover glass) of a display device, CS of the glass substrate is preferably 700MPa to 850 MPa.

In order to prevent damage even when the glass substrate collides with a sharp object, the depth of the compressive stress layer (hereinafter referred to as dol) of the glass substrate is preferably 15 μm or more, more preferably 20 μm or more, and even more preferably 25 μm or more. On the other hand, in order to eliminate the risk that the glass substrate cannot withstand the compressive stress of itself and is naturally damaged, the DOL of the glass substrate is preferably 150 μm or less, more preferably 100 μm or less, still more preferably 80 μm or less, and particularly preferably 60 μm or less.

In particular, when the cover member according to the present embodiment is used as a cover member (cover glass) of a display device, the DOL of the glass substrate is preferably 25 μm or more and 60 μm or less.

The glass matrix contains Li ₂ In the case of O, the strength can be further improved by performing the chemical strengthening treatment 2 or more times.

Specifically, for example, in the first treatment, for example, the glass substrate is brought into contact with an inorganic salt composition mainly containing sodium nitrate salt, and ion exchange between Na and Li is performed. Next, in a second treatment, for example, the glass substrate is contacted with an inorganic salt composition mainly containing potassium nitrate, and ion exchange between K and Na is performed. This is preferable because a compressive stress layer having a deep DOL and a high surface stress can be formed.

The thickness of the transparent substrate can be appropriately selected according to the application. For example, in the case of a resin substrate, a glass substrate, or the like, the thickness is preferably 0.1 to 5mm, more preferably 0.2 to 2mm.

When the chemical strengthening treatment is performed using a glass substrate as the transparent substrate 1, the thickness of the glass substrate is usually preferably 5mm or less, more preferably 3mm or less, in order to effectively perform the chemical strengthening treatment.

In addition, the size of the transparent substrate can be appropriately selected according to the application. In the case of using as a cover glass for a display device, the dimensions are preferably 50mm×100mm to 2000×1500mm, and the thickness is preferably 0.5 to 4mm.

The transparent substrate may have a curved shape such as a substrate having one or more curved portions, as well as a flat shape. For example, recently, among various devices including an image display device such as a television, a personal computer, a smart phone, and car navigation, a device in which a display surface of the image display device is curved has been developed. In the case where the transparent substrate is in a shape having a curved surface, the cover member can be suitably used as a cover member of such an image display device.

In the case where the transparent substrate has a curved surface, the surface of the transparent substrate may be entirely formed of the curved surface, or may be formed of a curved portion and a flat portion. Examples of the case where the entire surface is formed of a curved surface include a case where the cross section of the transparent substrate is circular arc-shaped.

When the transparent substrate has a curved surface, the radius of curvature (hereinafter also referred to as "R") thereof can be appropriately set according to the application, type, and the like of the transparent substrate, and is not particularly limited. For example, R is preferably 25000mm or less, more preferably 1mm to 5000mm, particularly preferably 5mm to 3000mm. When R is not more than the upper limit, the product is more excellent in appearance than a flat plate. When R is equal to or greater than the lower limit, the antifouling layer 2 and the print layer 3 can be uniformly formed on the curved surface.

The surface of the transparent substrate may be subjected to antiglare treatment. In the case where the transparent substrate is a glass substrate, a rugged structure may be formed on one main surface of the glass substrate by a spray coating method in which a liquid containing silica fine particles is applied to the surface of the glass substrate, a frosting treatment (also referred to as antiglare treatment) in which the surface of the glass substrate is processed by etching, or the like, and antiglare property may be imparted.

The method of the polishing treatment is not particularly limited, and a known method, for example, a method described in international publication No. 2014/112297, or the like can be used.

[ antifouling layer ]

The stain-proofing layer 2 exhibits stain-proofing properties by having water repellency and oil repellency, and the material is not particularly limited as long as stain-proofing properties can be imparted to the first main surface 1A of the transparent substrate 1. For example, the stain-proofing layer 2 is preferably composed of a fluorine-containing organosilicon compound film obtained by curing a fluorine-containing organosilicon compound. Examples of the fluorine-containing organosilicon compound include fluorine-containing hydrolyzable silicon compounds. In the present specification, the fluorine-containing hydrolyzable silicon compound means a compound having a hydrolyzable group or a hydrolyzable silyl group in which an atom is bonded to a silicon atom and further having a fluorine-containing organic group bonded to the silicon atom. The hydrolyzable group or the combination of atoms bonded to the silicon atom to form a hydrolyzable silyl group is referred to as a "hydrolyzable group".

As the composition for forming the antifouling layer, a composition containing a fluorine-containing hydrolyzable silicon compound can be preferably used. Specifically, KP-801 (trade name, manufactured by Xinshi chemical industry Co., ltd.), X-71 (trade name, manufactured by Xinshi chemical industry Co., ltd.), KY-130 (trade name, manufactured by Xinshi chemical industry Co., ltd.), KY-178 (trade name, manufactured by Xinshi chemical industry Co., ltd.), KY-185 (trade name, manufactured by Xinshi chemical industry Co., ltd.), OPTOOL (registered trademark) DSX (trade name, manufactured by Dain industry Co., ltd.) and the like can be preferably used.

The fluorine-containing organosilicon compound-containing coating film can be obtained by depositing the composition for forming a coating film containing the fluorine-containing hydrolyzable silicon compound on the surface of a transparent substrate or the surface of an adhesion layer to be described later and reacting the deposited composition.

The thickness of the antifouling layer is not particularly limited, but is preferably 2nm or more in order to improve uniformity and abrasion resistance. On the other hand, in order to improve the optical characteristics such as haze value of the cover member, the thickness of the antifouling layer is preferably 20nm or less, more preferably 15nm or less, and still more preferably 10nm or less.

Examples of the method for forming the antifouling layer include wet methods such as spin coating, dip coating, casting, slit coating and spray coating, vapor deposition, and the like. In order to obtain a film having high adhesion to a transparent substrate or an adhesion layer described later, the stain-proofing layer is preferably formed by a vacuum vapor deposition method.

The first main surface 1A of the transparent substrate 1 in the present embodiment preferably has substantially no antifouling layer at least in a part of the portion to which the adhesive member 4 adheres. The adhesive member is adhered to a portion having no antifouling layer, thereby obtaining a higher adhesive strength.

The term "substantially no antifouling layer" means that the number of peaks (cps) of fluorine atoms (F) is 62% or less of the region where the antifouling layer is present when the composition analysis of the surface is performed by a μ -X-ray photoelectron spectroscopy device.

The method of forming the region where the antifouling layer is not particularly limited, and known methods such as masking, laser engraving, corona discharge, plasma, and laser cleaning can be used. More specifically, for example, the antifouling layer may be formed in a state where a portion where the antifouling layer is not to be formed is masked with a tape or the like, and then the tape or the like is removed to form a region where the antifouling layer is not present. As the tape or the like, a PET tape, a polyimide tape or the like is preferably used.

Further, as described in patent document 1, an antifouling layer may be formed on the entire first main surface of the transparent substrate, and then the antifouling layer may be partially removed by laser, plasma, or the like, thereby forming a region where the antifouling layer is not present. In this case, for example, the portion where the antifouling layer is not to be removed is masked with a sheet having heat resistance such as glass, alumina, bakelite, or the like, and then the antifouling layer can be partially removed by a treatment with a laser, plasma, or the like.

[ adhesion layer ]

In order to ensure the adhesion of the stain-proofing layer 2, the covering member of the present embodiment may have an adhesion layer between the transparent substrate and the stain-proofing layer. From the viewpoint of adhesion to the stain-proofing layer, the outermost layer of the adhesion layer on the stain-proofing layer side is preferably a layer containing silicon oxide as a main component.

The surface roughness of the layer in contact with the stain-proofing layer of the adhesion layer is preferably 3nm or less, more preferably 2nm or less, and still more preferably 1.5nm or less, based on the arithmetic average roughness (Ra). When Ra is 3nm or less, the coating is sufficiently smooth, so that scratch between the cloth and the antifouling layer can be suppressed, and abrasion resistance can be improved.

In addition, for example, when the first main surface 1A has a concave-convex shape by the antiglare treatment, the measurement region may be set so as not to include the concave-convex shape when measuring the arithmetic average roughness (Ra) of the adhesion layer. The Ra of the adhesion layer can be measured by setting the measurement region to a region other than the ridge line of the irregularities, for example.

In addition, for example, when the first main surface 1A of the transparent substrate 1 has a concave-convex shape by the antiglare treatment, the root mean square roughness (Rq) of the layer in contact with the antifouling layer of the adhesion layer is preferably 10nm or more, more preferably 20nm or more. The Rq is preferably 1500nm or less, more preferably 1000nm or less, still more preferably 500nm or less, particularly preferably 200nm or less. When Rq is in the above range, not only the peeling of the antifouling layer can be suppressed and the abrasion resistance can be improved, but also the anti-glare property and the antiglare property can be achieved. In measuring the Rq of the concave-convex shape, the measurement region may be selected so as to sufficiently include the concave-convex shape of the first main surface, contrary to the measurement of the arithmetic average roughness (Ra) of the adhesion layer. Further, since the surface roughness of the adhesion layer and the antifouling layer is sufficiently smooth, it is considered that the value of Rq measured by the above method is the same as the value of Rq of the uneven shape in the state where the adhesion layer and the antifouling layer are provided. The method for forming the adhesion layer is not particularly limited, and the adhesion layer can be formed by the same method as in the case of forming a layer containing silicon oxide as a main component in a low-reflection layer described later.

[ Low reflection layer ]

The low reflection layer is a film that can improve the transmittance of light from a display device or the like and improve the visibility of the display device or the like, in addition to the effect of reducing the reflectance and glare caused by reflection of light.

The cover member of the present embodiment preferably includes a low reflection layer between the first main surface of the transparent substrate and the stain-proofing layer. The low reflection layer is not particularly limited as long as it can suppress reflection of light, and may be a structure in which a high refractive index layer having a refractive index of 1.9 or more at a wavelength of 550nm and a low refractive index layer having a refractive index of 1.6 or less at a wavelength of 550nm are laminated. The low reflection layer may include only 1 low refractive index layer.

The low reflection layer may have a structure including 1 layer, or may have a structure including 2 or more layers each of the high refractive index layer and the low refractive index layer. When the high refractive index layer and the low refractive index layer are contained in 2 or more layers, the low reflective layer is preferably a structure in which the high refractive index layer and the low refractive index layer are alternately laminated.

In order to enhance the effect of reducing the reflectance, the low-reflection layer is preferably a laminate of a plurality of layers. For example, the laminate is preferably a laminate in which 2 or more and 10 or less layers are laminated as a whole, more preferably 2 or more and 8 or less layers are laminated, and still more preferably 4 or more and 6 or less layers are laminated. The laminate here is preferably a laminate in which a high refractive index layer and a low refractive index layer are laminated as described above.

The materials of the high refractive index layer and the low refractive index layer are not particularly limited, and can be appropriately selected in consideration of the degree of the effect of reducing the reflectance required, productivity, and the like. As a material constituting the high refractive index layer, for example, a material selected from niobium oxide (Nb ₂ O ₅ ) Titanium oxide (TiO) ₂ ) Zirconium oxide (ZrO) ₂ ) Tantalum oxide (Ta) ₂ O ₅ ) Silicon nitride (Si) ₃ N ₄ ) More than 1 selected from the group consisting of a plurality of materials. As a material constituting the low refractive index layer, a material selected from silicon oxide (SiO ₂ ) More than 1 kind of material containing mixed oxide of Si and Sn, material containing mixed oxide of Si and Zr, and material containing mixed oxide of Si and Al.

From the viewpoint of productivity and refractive index, the high refractive index layer is preferably a layer containing 1 kind selected from niobium oxide, tantalum oxide and silicon nitride as a main component, and the low refractive index layer is preferably a layer containing silicon oxide as a main component.

In addition, the low reflection layer can also be used as an adhesion layer by using silicon oxide as the main component of the outermost layer of the low reflection layer.

The low reflection layer is preferably formed by a dry film forming method. Examples of the dry film forming method include a vapor deposition method, an ion beam assisted vapor deposition method, an ion plate method, a sputtering method, and a plasma CVD method. Among them, the vapor deposition method or the sputtering method is preferably used.

[ adhesive Member ]

The adhesive member 4 is, for example, a frame such as a push button, a switch, a dial, or a meter, or a decorative member such as a logo or a mark. As a material of the adhesive member 4, for example, a resin material, a metal material, a rubber material, or the like can be used.

The shape of the adhesive member is not particularly limited, and is, for example, a circular shape, an elliptical shape, a quadrangular shape, a ring shape, or the like.

The adhesive used for bonding the adhesive member 4 is not particularly limited, and for example, epoxy-based, cyanoacrylate-based, thermosetting resin-based, elastomer-based adhesives and the like can be used. The type of the adhesive is not particularly limited as long as it can bond the glass article and the adhesive member, and is preferably a type excellent in durability.

The adhesive member may be mounted such that the entire adhesive member is located on the cover member when the cover member is viewed from the stain-proofing layer side, or may be mounted such that only a part of the adhesive member is located on the cover member. That is, when the cover member is viewed from the stain-proofing layer side, a part of the adhesive member may be located outside the cover member.

In the case where the adhesive member is a member having a function of transmitting information that has been operated, such as a push button, a switch, a dial, or the like, the method of transmitting information is not particularly limited. For example, the information may be transmitted to a receiving device located on the back side of the transparent substrate via magnetic force or electrostatic force, or may be transmitted via wiring. In the case of using the wiring, it is preferable that a part of the adhesive member is located outside the covering member. This is because wiring can be easily hidden.

[ printing layer ]

The cover member 10 in the present embodiment includes the printed layer 3 on at least a part of the second main surface 1B of the transparent substrate 1. The printed layer 3 may be a light shielding portion that shields a portion that gets into a visual field and becomes an obstacle when viewing the display, such as a wiring circuit disposed on the outer peripheral portion of the display panel, for example, to improve the visibility and the appearance of the display, or may be a printed portion such as a letter or a pattern.

The printing layer is a layer formed by a printing ink method. Examples of the printing method include bar coating, reverse coating, gravure coating, die coating, roll coating, screen coating, and ink jet method. Since printing can be performed not only simply but also on various substrates, and printing can be performed according to the size of the substrate, the printing method is preferably a screen printing method or an inkjet method.

The type of ink is not particularly limited, and for example, an inorganic ink containing a ceramic fired body or the like, or an organic ink containing a coloring material such as a dye or pigment and an organic resin can be used.

Examples of the ceramics contained in the inorganic ink include oxides such as chromium oxide and iron oxide, carbides such as chromium carbide and tungsten carbide, carbon black, mica, and the like. The printing portion is obtained by, for example, melting the inorganic ink composed of the ceramics and silica, printing the melted ink on the second main surface 1B of the transparent substrate 1 in a desired pattern, and then firing the melted ink. Such inorganic inks require a melting and firing step and are generally used as glass-dedicated inks.

The organic ink is a composition containing a dye or pigment and an organic resin. Examples of the organic resin include resins composed of homopolymers such as epoxy resins, acrylic resins, polyethylene terephthalate, polyether sulfone, polyarylate, polycarbonate, transparent ABS resins, phenolic resins, acrylonitrile-butadiene-styrene resins, polyurethane, methyl methacrylate, polyethylene, polyvinyl butyral, polyether ether ketone, polyethylene, polyester, polypropylene, polyamide, polyimide, and the like, and resins composed of copolymers of monomers and copolymerizable monomers of these resins. The organic resin may be a mixture of the above resins. The dye or pigment may be used without particular limitation as long as it has light-blocking properties.

Among the inorganic ink and the organic ink, the organic ink is preferable because the firing temperature is low. In addition, from the viewpoint of chemical resistance, organic inks containing pigments are preferable.

The print layer may be a multilayer formed by stacking a plurality of layers, or may be a single layer. The multilayered printed layer can be formed by repeating printing and drying of the ink.

The thickness of the printed layer is not particularly limited, but is preferably 2 μm or more, more preferably 5 μm or more, from the viewpoint of obtaining sufficient light-shielding properties. On the other hand, from the viewpoint of suppressing the mixing of bubbles when attaching to a display or the peeling caused by the internal stress of the printed layer, the thickness of the printed layer is preferably 50 μm or less, more preferably 30 μm or less.

[ relation between printed layer and adhesive Member ]

In the cover member of the present embodiment, the adhesive member contact portion projection area is defined as follows.

The adhesive member contact portion projection region is a region in which the adhesive member is substantially in contact with the transparent substrate or the stain-proofing layer is projected onto the second main surface in parallel with the thickness direction of the transparent substrate. The region where the adhesive member substantially contacts the transparent substrate or the stain-proofing layer is a concept including not only a region where the adhesive member is in close contact with the transparent substrate or the stain-proofing layer, but also a region where a distance (a distance in a direction perpendicular to the first main surface) from the adhesive member to the transparent substrate or the stain-proofing layer is 1mm or less.

The area from the boundary of the projected area of the adhesive member contact portion to the portion 1000 μm inward from the boundary of the area was defined as the boundary vicinity area.

An inner region is defined as a region 500 μm or more inward from the boundary of the projected region of the adhesive member contact portion.

In the case where a region where the adhesive member is substantially in contact with the transparent substrate or the stain-proofing layer is present, the region where the stain-proofing layer is substantially absent is projected onto the second main surface parallel to the thickness direction of the transparent substrate, and the region where the stain-proofing layer is substantially absent is referred to as a stain-proofing layer absent portion projected region.

The relationship between these areas and the printed layer will be described in detail below. First, as examples of the covering member according to the present embodiment, a plurality of modes are described with reference to the drawings.

As a first embodiment, the shape of the adhesive member 104 is described by taking the shape of the circular cover member 110 as viewed from the antifouling layer side.

Fig. 3 shows a plan view of the first embodiment of the cover member 110 as seen from the stain-proofing layer side, fig. 4 shows an enlarged view of the periphery of the adhesive member 104 in a cross-sectional view taken along the line B-B in fig. 3, and fig. 5 shows an enlarged view of the periphery of the adhesive member 104 of the first embodiment of the cover member 110 as seen from the printing layer side.

The broken line X in fig. 5 is a line obtained by projecting the boundary line of the region where the adhesive member 104 substantially contacts the transparent substrate 101 or the stain-proofing layer 102 onto the second main surface 101B of the transparent substrate 101 in parallel with the thickness direction of the transparent substrate 101. That is, the area (the area inside the broken line X) divided by the broken line X is the adhesive member contact portion projection area.

The broken line Y in fig. 5 is a line indicating a portion 1000 μm inward from the boundary (i.e., broken line X) of the projection area of the contact portion of the adhesive member. That is, the region from the broken line X to the broken line Y is a boundary vicinity region.

The broken line Z in fig. 5 is a line indicating a portion 500 μm inward from the boundary (i.e., broken line X) of the projection area of the contact portion of the adhesive member. That is, the region (region inside the broken line Z) divided by the broken line Z is an inside region.

The projection area of the non-existing portion of the anti-fouling layer is not shown. The same applies to the following examples.

As a second embodiment, the shape of the adhesive member 204 is described by taking the shape of a cover member 210 having a ring shape (hereinafter also referred to as an "annular shape") when viewed from the antifouling layer side.

Fig. 6 shows a plan view of the second embodiment of the cover member 210 as seen from the stain-proofing layer side, fig. 7 shows an enlarged view of the periphery of the adhesive member 204 in a cross-sectional view taken along the line C-C in fig. 6, and fig. 8 shows an enlarged view of the periphery of the adhesive member 204 of the second embodiment of the cover member 210 as seen from the printing layer side.

The broken lines X1 and X2 in fig. 8 are lines obtained by projecting the boundary line of the region where the adhesive member 204 substantially contacts the transparent substrate 201 or the stain-proofing layer 202, in parallel with the thickness direction of the transparent substrate 201, onto the second main surface 201B of the transparent substrate 201. That is, the area from the broken line X1 to the broken line X2 is the adhesive member contact portion projection area.

The broken line Y1 in fig. 8 is a line indicating a portion 1000 μm inward from the boundary (i.e., broken line X1) of the outer side of the projection area of the contact portion of the adhesive member. The broken line Y2 is a line indicating a portion 1000 μm inward from the boundary (i.e., the broken line X2) of the adhesive member contact portion projected area. That is, in the second embodiment, the region in which the region from the broken line X1 to the broken line Y1 and the region from the broken line X2 to the broken line Y2 are combined is the boundary vicinity region.

The broken line Z1 in fig. 8 is a line indicating a portion 500 μm inward from the boundary (i.e., broken line X1) outside the projection area of the contact portion of the adhesive member. The broken line Z2 is a line indicating a portion 500 μm inward from the boundary (i.e., the broken line X2) of the adhesive member contact portion projected area. That is, in the second embodiment, the area from the broken line Z1 to the broken line Z2 is the inner area.

As shown in fig. 5 and 8, the cover member of the present embodiment is provided with a region where the printed layer does not exist in the inner region. That is, in the cover member of the present embodiment, at least a part of the inner region is not provided with a print layer. Thus, even when a load is applied to the adhesive member and a stress is locally applied to the projected area of the adhesive member contact portion on the second main surface, a strong tensile stress can be suppressed from being applied to the printed layer. Therefore, cracking or breaking is less likely to occur in the printed layer.

As described above, by providing the region where the printed layer is not present inside the projection region of the contact portion of the adhesive member, cracking and breaking of the printed layer can be suppressed. However, if the printed layer is not present near the boundary of the projection area of the contact portion of the adhesive member, there is a risk that the printed layer will be seen when the periphery of the adhesive member is viewed from an oblique direction, and the appearance will be impaired.

Therefore, as shown in fig. 5 and 8, the covering member of the present embodiment is provided with a region in which the print layer is present in the vicinity of the boundary. That is, in the cover member of the present embodiment, at least a part of the boundary vicinity area is provided with the print layer. This suppresses the risk of visually recognizing the gaps in the printed layer and thereby detracting from the aesthetic appearance.

In order to improve the appearance, the area in the vicinity of the boundary is preferably 10 μm or less, more preferably 50 μm or less, still more preferably 100 μm or less, and the entire area is preferably provided with a printed layer, from the boundary of the projection area of the contact portion of the adhesive member (i.e., the broken line X in fig. 5, and the broken lines X1 and X2 in fig. 8).

On the other hand, the boundary vicinity is a region which is visually attractive in the left and right, but is also a region in which stress is particularly likely to act when a load is applied to the adhesive member. Therefore, in order to suppress cracking or breakage of the printed layer, it is preferable that at least a part of the area near the boundary is not provided with the printed layer.

In addition, since the adhesive member is adhered to the first main surface of the transparent substrate particularly in the region where the stain-proofing layer is removed, stress is particularly easily applied to the second main surface when a load is applied to the adhesive member. Therefore, the projected area of the antifouling layer non-existing portion is preferably provided with no printing layer at least in part, and more preferably provided with no printing layer in the whole area. In particular, when the antifouling layer non-existing portion projection area is included in the inner area, it is preferable that the portion of the antifouling layer non-existing portion projection area included in the inner area does not include the printing layer. The projected area of the non-existing portion of the antifouling layer may be partially or entirely included in the inner area.

As the first and second aspects described above, an example is shown in which a print layer is formed in a band shape along an end portion of a transparent substrate when viewed from a surface on the stain-proofing layer side, and an adhesive member is accommodated in a width direction of the print layer. However, in the cover member according to the present embodiment, the adhesive member may not be accommodated in the width direction of the printed layer as in the third to sixth embodiments described below. That is, a part of the adhesive member may be formed outside the printed layer when viewed from the surface on the stain-proofing layer side. Fig. 9 shows a plan view of the cover member 310 according to the third embodiment as viewed from the antifouling layer side. Fig. 10 is an enlarged view of the periphery of the adhesive member 304 of the cover member 310 of the third embodiment as viewed from the printed layer side. The broken lines X1, X2, Y1, Y2, Z1, and Z2 shown in fig. 10 are the same as the second embodiment shown in fig. 8.

The third embodiment is an example in which a part of the adhesive member 304 is located outside the end portion of the printed layer 303 in the cover member inner direction when viewed from the surface on the stain-proofing layer side. In the third aspect, the adhesive member is an example of a ring shape when viewed from the surface of the cover member on the side of the stain-proofing layer. In the case where the adhesive member is annular in shape, as shown in fig. 10, it is preferable that at least a part of the inner region is provided with a portion continuously having no print layer along the circumferential direction of the ring.

As the cover member 410 of the fourth embodiment, an example will be described in which a part of the adhesive member 404 is located outside the cover member when viewed from the stain-proofing layer side.

Fig. 11 shows a plan view of the fourth cover member 410 viewed from the stain-proofing layer side, fig. 12 shows an enlarged view of the periphery of the adhesive member 404 in a cross-sectional view taken along line D-D in fig. 11, and fig. 13 shows an enlarged view of the periphery of the adhesive member 404 of the fourth cover member 410 viewed from the printing layer side.

The broken lines X1, X2, Y1, Y2, Z1, and Z2 shown in fig. 13 are the same as the second embodiment shown in fig. 8.

In the second main surface 401B of the transparent substrate 401, a portion 50 μm inward from the outer peripheral end is shown by a broken line W. In the second main surface 401B, a region from the outer peripheral end to a portion 50 μm inward from the outer peripheral end (i.e., a portion shown by a line W) is defined as a region near the outer peripheral end.

As in the fourth embodiment, when a part of the adhesive member 404 is located outside the cover member when viewed from the stain-proofing layer side, at least a part of the outer peripheral end vicinity region and the inner region may overlap. In the case where a load is applied to the adhesive member, a particularly strong stress is applied to the overlapped portion. Therefore, the overlapping portion is preferably not provided with a print layer. That is, when a part of the inner region is included in the vicinity of the outer peripheral end, it is preferable that the part of the inner region included in the vicinity of the outer peripheral end is not provided with a print layer.

In the second main surface 401B, it is more preferable that the printed layer is not provided in a portion where a region from the outer peripheral end to a portion 100 μm inward from the outer peripheral end overlaps with the inner region. Further, in the second main surface 401B, it is preferable that the region from the outer peripheral end to the portion 200 μm inward from the outer peripheral end overlaps with the inner region, and the printed layer is not provided. In the second main surface 401B, it is particularly preferable that the region from the outer peripheral end to the portion 500 μm inward from the outer peripheral end and the portion where the inner region overlaps are not provided with a print layer. In the second main surface 401B, it is most preferable that the region from the outer peripheral end to the portion 1000 μm inward from the outer peripheral end overlaps with the inner region, and the printed layer is not provided.

In particular, it is preferable that the portion where the peripheral end vicinity region and the boundary vicinity region overlap does not include a print layer. With such a structure, the stress generated at the outer peripheral end of the printed layer can be reduced more reliably.

A preferred example of the structure in which the printed layer is formed in a band shape along the end portion of the transparent substrate and the projected area of the adhesive member contact portion includes one end portion and the other end portion in the width direction of the printed layer is described as the cover member 510 of the fifth embodiment.

Fig. 14 shows a plan view of the fifth cover member 510 viewed from the stain-proofing layer side, fig. 15 shows an enlarged view of the periphery of the adhesive member 504 in a cross-sectional view taken along the line E-E in fig. 14, and fig. 16 shows an enlarged view of the periphery of the adhesive member 504 of the fifth cover member 510 viewed from the printed layer side.

The broken lines X, Y and Z shown in fig. 16 are the same as those in the first embodiment shown in fig. 5.

In such a configuration, as shown in fig. 16, it is preferable that there is a portion in which the printing layer is continuously not provided between one end portion and the other end portion in the width direction of the printing layer included in the projection area of the contact portion of the adhesive member. That is, the adhesive member contact portion projection region preferably has a portion not having a print layer formed continuously between one end portion and the other end portion in the width direction of the print layer. By forming such a portion not provided with a print layer, the print layer becomes discontinuous in the longitudinal direction (direction perpendicular to the width direction). This reduces stress applied to the printed layer.

In the fifth aspect, the adhesive member is circular in shape as viewed from the antifouling layer side of the cover member, but the same applies to the case where the adhesive member is annular in shape. As a sixth aspect, an example will be described in which the adhesive member has a ring shape in a configuration in which one end portion and the other end portion in the width direction of the printed layer are included in the projection area of the contact portion of the adhesive member.

Fig. 17 shows a plan view of the sixth embodiment of the cover member 610 seen from the stain-proofing layer side, fig. 18 shows an enlarged view of the periphery of the adhesive member 604 in a cross-sectional view taken along the line F-F in fig. 17, and fig. 19 shows an enlarged view of the periphery of the adhesive member 604 of the sixth embodiment of the cover member 610 seen from the printing layer side.

The broken lines X1, X2, Y1, Y2, Z1, and Z2 shown in fig. 19 are the same as the second embodiment shown in fig. 8. The broken line W is the same as that of the fourth embodiment shown in fig. 13.

In this example, as in the fifth aspect, it is also preferable that there is a portion in which the printing layer is continuously not provided between one end portion and the other end portion in the width direction of the printing layer included in the projection area of the contact portion of the adhesive member. As described using the fourth aspect, it is preferable that the portion where the outer peripheral end vicinity region overlaps the inner region does not include a print layer.

The above description has been given by taking a plurality of examples, but the cover member of the present embodiment is not limited to these. For example, in the above example, the case where the shape of the adhesive member is circular and annular has been described, but the shape of the adhesive member may be another shape. Other embodiments, which are appropriately modified within the scope of the gist of the present invention, are also included in the scope of the present invention.

< second embodiment >

[ cover Member ]

The cover member of the second embodiment includes a transparent substrate, an antifouling layer, and a print layer. The transparent substrate has a first main surface and a second main surface. The stain-proofing layer is formed on at least a portion of the first major surface of the transparent substrate. The printed layer is formed on at least a portion of the second major surface of the transparent substrate.

The cover member of the present embodiment is used by being bonded to the surface on the side of the stain-proofing layer by an adhesive member. That is, the cover member of the present embodiment is a cover member at a previous stage of bonding the adhesive member.

The preferred structures of the transparent substrate, the stain-proofing layer, the printed layer, the adhesive member to be adhered later, and the adhesion layer and the low reflection layer as optional components are the same as those of the first embodiment.

The cover member of the second embodiment has a portion partially without a print layer, similar to the cover member of the first embodiment. In the first embodiment, the preferred embodiment of the portion not provided with the printing layer is defined using the positional relationship with the adhesive member, but in the second embodiment, the preferred embodiment of the portion not provided with the printing member is different from the first embodiment in the defining method of the portion not provided with the adhesive member.

The following is a detailed description.

In the second embodiment, the first main surface of the transparent substrate has a region where the antifouling layer is substantially absent. The meaning of "substantially no" is the same as that of the first embodiment. A part or the whole of the region where the antifouling layer is substantially absent becomes a part to be bonded to the adhesive member later. Therefore, in the second embodiment, a preferable mode of defining the portion not provided with the print layer is defined using the positional relationship with the region where the antifouling layer is substantially absent.

In the second embodiment, the area of the first main surface of the transparent substrate where the antifouling layer is substantially absent is set as the antifouling layer absent portion projection area, the area being obtained by projecting the antifouling layer onto the second main surface so as to be parallel to the thickness direction of the transparent substrate. The definition is the same as that of the first embodiment.

In the second embodiment, the region of the antifouling layer non-existing portion projection region located 500 μm or more inward from the boundary of the region is set as the inner region.

In the second embodiment, at least a part of the inner region is provided with no print layer.

In the second embodiment, the region where the antifouling layer is substantially absent and the region to which the adhesive member is adhered thereafter substantially coincide. Therefore, the projected area of the non-existing portion of the anti-fouling layer in the second embodiment is a portion where a large stress can be locally generated when a load is applied to the adhesive member after the adhesive member is attached. Therefore, in the second embodiment, since at least a part of the inner region is not provided with the printed layer, when the adhesive member is adhered later, the printed layer is less likely to generate cracks or breaks, as in the first embodiment.

The shape of the projected area of the adhesive member where no portion exists, that is, the shape of the area of the first main surface where the antifouling layer is substantially not present, may be appropriately set according to the shape of the adhesive member, and may be, for example, a circular shape, an elliptical shape, a quadrangular shape, a ring shape, or the like.

As in the first embodiment, the projected area of the portion where the stain-proofing layer is not present preferably has no print layer in at least a part thereof, and more preferably has no print layer in the entire area.

In the case where the projected area of the adhesive member non-existing portion is annular, it is preferable that at least a part of the inner area is provided with a portion continuously having no print layer along the circumferential direction of the annular.

In the second embodiment, when at least a part of the projection area of the portion where the stain-proofing layer is not present overlaps with the area near the outer peripheral end, the overlapping portion is preferably not provided with a print layer. That is, when a part of the antifouling layer non-existing portion projection area is included in the peripheral end vicinity area, it is preferable that the part of the antifouling layer non-existing portion projection area included in the peripheral end vicinity area does not include a print layer. In the second main surface, it is more preferable that the printed layer is not provided in a portion where a region from the outer peripheral end to a portion 100 μm inward from the outer peripheral end overlaps with a projected region of the non-contamination layer-existing portion. Further, it is preferable that the printed layer is not provided in a portion where a region from the outer peripheral end to a portion 200 μm inward from the outer peripheral end overlaps with a projected region of the non-contamination layer-existing portion. In addition, it is particularly preferable that the printed layer is not provided in a portion where a region from the outer peripheral end to a portion 500 μm inward from the outer peripheral end overlaps with a projected region of the non-contamination layer-existing portion. Further, it is most preferable that the printed layer is not provided in a portion where a region from the outer peripheral end to a portion 1000 μm inward from the outer peripheral end overlaps with a projected region of the non-contamination layer-existing portion.

In the structure in which the print layer is formed in a band shape along the end portion of the transparent substrate, and the antifouling portion projection area includes one end portion and the other end portion in the width direction of the print layer, as in the first embodiment, it is preferable that a portion in which the print layer is continuously not provided between the one end portion and the other end portion in the width direction of the print layer included in the antifouling portion projection area is present.

Examples

The present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless the gist thereof is exceeded. Examples 1 to 3 are examples, and example 4 is a comparative example.

Example 1

(formation of printing layer)

A printed layer was formed on a region from an end to 50mm inward of the end of the second main surface of a 250mm by 350mm by 1.3mm glass substrate (manufactured by AGC Co., ltd.). However, no printed layer was formed on the entire area of the second main surface, which will be described later, from the boundary of the projected area of the contact portion of the adhesive member to the inner side of 1000 μm of the boundary.

Printing was performed by screen printing in the following order to form a black printed layer. First, a black ink (trade name: GLS-HF, manufactured by Imperial ink manufacturing Co., ltd.) was applied to a thickness of 3 μm by means of a screen printer. Thereafter, the resultant was kept at 150℃for 10 minutes to dry it, thereby forming a first printed layer. Next, the same black ink as described above was applied to a thickness of 3 μm in the same order as described above on the first printed layer. Thereafter, the resultant was dried at 150℃for 40 minutes to form a second printed layer. Thus, a glass substrate having a black printed layer in which the first printed layer and the second printed layer are laminated and a printed layer provided on the outer peripheral portion of the second main surface was obtained.

(formation of adhesion layer)

On the first main face of the glass substrate,SiO is formed as a contact layer ₂ And (3) a film. SiO (SiO) ₂ The film was sputtered by magnetron sputtering using Si target in Ar/O ₂ Film formation is performed in an ambient atmosphere. The film thickness was set to 10nm.

(formation of antifouling layer)

Next, an antifouling layer is formed on the first main surface. First, as a material of the antifouling layer, a material for forming a fluorine-containing organosilicon compound coating film is introduced into a heating vessel. Thereafter, the inside of the heating vessel was degassed by a vacuum pump for 10 hours or more to remove the solvent from the material solution, thereby forming a composition for forming a fluorine-containing organosilicon compound coating film (hereinafter referred to as a coating film-forming composition). KY-185 (manufactured by Xinyue chemical industry Co., ltd.) was used as a composition for forming a coating.

Next, the heating vessel to which the film-forming composition was added was heated to 270 ℃. After the temperature reached 270 ℃, this state was maintained for 10 minutes until the temperature was stable. Next, the glass substrate on which the printing layer and the adhesion layer were formed was set in a vacuum chamber. Then, the film-forming composition is supplied from a nozzle connected to a heating vessel containing the film-forming composition, toward the first main surface of the glass substrate, and film formation is performed.

While measuring the film thickness by a quartz oscillator monitor provided in a vacuum chamber, film formation was performed until the film thickness of the fluorine-containing organosilicon compound coating film on the adhesion layer became 4nm. Thereafter, the glass substrate is taken out of the vacuum chamber.

(bonding of bonding Member)

Next, an annular adhesive member (outer diameter 70mm, inner diameter 40mm, material: ABS resin) was bonded to the first main surface so that the right end of the adhesive member was located 20mm inward from the right end of the first main surface of the glass substrate, to obtain a covering member of example 1. As an adhesive, polysulfide SS-310 (manufactured by Shimadzu rubber Co., ltd.) was used and the adhesive was fixed at room temperature for 20 hours. At this time, the adhesive member was adhered after removing the anti-fouling layer in the entire region of 500 μm or more inside the boundary line of the adhesive member at the attachment position of the adhesive member on the first main surface under the following conditions.

(conditions for removing stain-proofing layer)

Mask is used: a glass mask having a thickness of 0.7mm and having an opening in the shape of an antifouling layer removed region was placed on the first main surface in an overlapping manner, and the following atmospheric pressure plasma treatment was performed. Separately from the above-described glass mask, a circular glass mask is placed at a portion of the center portion of the annular region where the anti-fouling layer is not removed. The mask material is not limited to glass, and any sheet having heat resistance such as alumina or bakelite can be used.

The using device comprises: plasma irradiator PS-1200AW manufactured by Wedge Co., ltd

The gas is used: air

Frequency: 50Hz

And (3) outputting: 1200W

Handpiece speed, number of treatments: 20 mm/Sec.times.4 round trip

Distance between glass-plasma irradiation ports: 5mm of

(evaluation of surface F amount)

The amount of surface F of the inner region excluding 1.5mm of the peripheral portion was examined in the region from which the anti-fouling layer was removed, that is, the region subjected to the atmospheric pressure plasma treatment of the glass mask. The F amount (F-count) of the area where the anti-fouling layer was not removed was 0.193kcps. In contrast, the F content (F-count) of the inner region excluding 1.5mm of the peripheral portion of the region from which the anti-fouling layer was removed was 0.120kcps or less. The F content is 62% or less compared with the case where the F content of the region where the stain-proofing layer is not removed is 100%.

Measurement conditions of the μ -X-ray photoelectron spectroscopy apparatus are as follows.

Measuring device: scanning mu-X-ray photoelectron spectrum analyzer Quantum SXM manufactured by ULVAC-PHI company

An X-ray source: al K alpha 100 μm,25W,15kV

Measurement conditions: pass energy=224 [ ev ], energy step=0.4 [ ev/step ],1cycle

Measuring angle: 45 ° point measurement

(evaluation of adhesive Strength)

Next, the adhesive strength of the adhesive member was evaluated under the following conditions. In the case of evaluating the adhesive strength of the adhesive member of each example, as a comparison, a sample to which the adhesive member was adhered was prepared in the same procedure as described above except that the antifouling layer was not removed.

Evaluation device: posiTest AT-A (manufactured by DeFelsko Co., ltd.)

And (3) clamping: made of aluminum metal, 20mm phi

Primer for clamp: polysulfide rubber primer No.70, manufactured by Cross creek rubber Co., ltd

Stretching speed: 0.2MPa/sec

As a result of the adhesive strength evaluation, the adhesive strength was about 0.75MPa in the sample to which the adhesive member was adhered without removing the antifouling layer. On the other hand, in example 1 in which the antifouling layer was removed under the above-described removal conditions, the adhesion strength was about 1.00MPa, which is excellent.

Fig. 20 shows a schematic view of the cover member of example 1 viewed from the printed layer side. The broken lines X1 and X2 in fig. 20 indicate the boundary lines of the projected areas of the contact portions of the adhesive members.

Example 2

A covering member of example 2 was obtained in the same manner as in example 1, except that the printed layer was formed in the region from the end of the second main surface to 25mm inside the end, and the adhesive member was bonded such that the right end of the adhesive member was located 5mm outside the right end of the first main surface of the glass substrate.

The F amount (F-count) of the inner region excluding 1.5mm of the peripheral portion of the region from which the anti-fouling layer was removed was 0.12kcps or less. The F content is 62% or less compared with the case where the F content of the region where the stain-proofing layer is not removed is 100%.

The adhesive strength of the adhesive member was about 1.00MPa, and was excellent.

Fig. 21 shows a schematic view of the cover member of example 2 viewed from the printed layer side. The broken lines X1 and X2 in fig. 21 indicate the boundary lines of the projected areas of the contact portions of the adhesive members.

Example 3

A printed layer was formed in a region 25mm inward from the end of the second main surface of the glass substrate as in example 1, and an anti-smudge layer was formed on the first main surface. In forming the print layer, as shown in fig. 22, a portion without the print layer is continuously formed between one end and the other end in the width direction of the print layer. The width of the portion not provided with the print layer was set to 5mm, and the center line in the width direction of the portion was passed through the center of a projection area of a contact portion of the adhesive member described later. Next, a disc-shaped adhesive member (outer diameter 40 mm) was adhered so that the right end of the adhesive member was located 5mm outside the right end of the first main surface of the glass substrate, to obtain a covering member of example 3. In this case, the adhesive member was adhered after the anti-fouling layer was removed in the whole of the rectangular region (circular region) which was inscribed in the region substantially in contact with the adhesive member and one side was shared with the outer peripheral end of the glass substrate, to obtain the covering member of example 3. The conditions for forming the print layer, forming the antifouling layer, and bonding the adhesive member were the same as in example 1 except for the above.

Fig. 22 shows a schematic diagram of the cover member of example 3 viewed from the printed layer side. The broken line X in fig. 22 indicates the boundary line of the projection area of the contact portion of the adhesive member.

Example 4

A printed layer was formed in a region 40mm inward from the end of the second main surface of the glass substrate as in example 1, and an anti-smudge layer was formed on the first main surface. Next, a disc-shaped adhesive member (outer diameter: 30 mm) was adhered so that the right end of the adhesive member was located 5mm inward from the right end of the first main surface of the glass substrate, to obtain a covering member of example 4. At this time, the adhesive member was adhered to the first main surface at the position where the adhesive member was attached, in the entire region 500 μm or more inward from the boundary line of the adhesive member, after removing the anti-fouling layer, to obtain the covering member of example 4. The conditions for forming the print layer, forming the antifouling layer, and bonding the adhesive member were the same as in example 1 except for the above.

Fig. 23 shows a schematic view of the cover member of example 4 viewed from the printed layer side. The broken line X in fig. 23 indicates the boundary line of the projection area of the contact portion of the adhesive member.

(evaluation)

The following operations (1) to (4) are performed on the covering members of each example.

(1) The cover member was vertically raised, and a weight of 5kg was applied to the adhesive member and held for 1 minute. After that, the weight was kept applied and rotated up and down for another 1 minute. This operation was repeated 50 times in total.

(2) The cover member was horizontally held so that the adhesive member was positioned above, and a weight of 5kg was placed on the adhesive member and held for 1 minute. After that, the weight was removed and held for 1 minute. This operation was repeated 50 times in total.

(3) Thermal cycling tests were performed. The thermal cycle test was performed by repeating 100 times a cycle in which the cover member was put into an environment of-40 ℃ for 30 minutes and then put into an environment of 85 ℃ for 30 minutes.

(4) The cover member was put into a damp heat tester and kept at 70℃for 100 hours in an atmosphere of 95% RH.

After that, the cover member was immersed in NaOH solution (ph=11) for 2 hours. Thus, when a crack is generated in the printed layer, naOH solution intrudes from the crack to dissolve the glass, so that the crack in the printed layer can be easily visually observed.

After that, the cover member was observed from the surface of the printed layer side and observed with a microscope (50 times), whether or not the peeling of the printed layer was confirmed, and the evaluation was performed according to the following criteria.

A: the peeling of the printed layer could not be confirmed by visual observation or microscopic observation.

B: the peeling of the printed layer was not confirmed by visual observation, but was confirmed by observation using a microscope.

C: the peeling of the printed layer can be confirmed by visual observation.

In the cover member of example 4 as a comparative example, peeling of the printed layer was visually confirmed (evaluation C).

In the cover member of example 3, the durability of the printed layer was high, but the peeling of the printed layer was confirmed by a microscope (evaluation B), although it was not confirmed by visual observation.

In the covering members of examples 1 and 2, the durability of the printed layer was particularly high, and peeling of the printed layer was not confirmed by visual inspection or microscopy (evaluation a).

In addition, in any of examples 1 to 3, the gaps of the printed layer were difficult to visually recognize even when the adhesive member was carefully observed from an oblique direction, and the appearance was excellent.

While the present application has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof. The present application is based on Japanese patent application No. 2019, 8-26 (patent application Ser. No. 2019-154124), the contents of which are incorporated herein by reference.

Description of the reference numerals

10. 110, 210, 310, 410, 510, 610, … cover the component; 1. 101, 201, 401, 501, 601, … transparent substrates; 1A, 101A, 201A, 401A, 501A, 601A …;1B, 101B, 201B, 401B, 501B, 601B …; 2. 102, 202, 402, 502, 602, … stain-proofing layer; 3. 103, 203, 303, 403, 503, 603, …; 4. 104, 204, 304, 404, 504, 604 … to bond the components; x, X1, X2 … adhesive member contact portion projection area boundary; y, Y1 and Y2 … are 1000 μm inward from the boundary of the projection area of the contact portion of the adhesive member; z, Z1 and Z2 … are 500 μm inward from the boundary of the projection area of the contact portion of the adhesive member; w … is located 500 μm inward from the outer peripheral end of the transparent substrate.

Claims

1. A cover member comprising a transparent substrate, an antifouling layer, a printing layer and an adhesive member, characterized in that,

the transparent substrate has a first major face and a second major face,

the stain-proofing layer is formed on at least a portion of the first major face,

the printed layer is formed on at least a portion of the second major face,

the adhesive member is adhered to one side of the stain-proofing layer,

a region obtained by projecting the adhesive member onto the second main surface so as to be parallel to the thickness direction of the transparent substrate in a region where the adhesive member is substantially in contact with the transparent substrate or the stain-proofing layer is defined as an adhesive member contact portion projection region,

The area from the boundary of the projection area of the contact portion of the adhesive member to the position 1000 μm inward from the boundary of the projection area is defined as a boundary vicinity area,

When an area 500 μm or more inside the boundary of the projection area of the adhesive member contact portion is set as an inside area,

at least a part of the boundary vicinity region is provided with the print layer, and at least a part of the inner region is not provided with the print layer.

2. The cover member of claim 1, wherein the cover member comprises a plurality of layers,

The first main surface of the transparent substrate further includes a region where the antifouling layer is substantially absent in a region where the adhesive member is substantially in contact with the transparent substrate or the antifouling layer,

when the area where the antifouling layer is substantially absent is projected onto the second main surface so as to be parallel to the thickness direction of the transparent substrate, the antifouling layer absent portion projection area is defined,

at least a part of the projected area of the non-existent portion of the stain-proofing layer is contained in the inner area,

the portion of the antifouling layer non-existing portion projection area included in the inner area is not provided with the print layer.

3. The cover member of claim 2, wherein the cover member comprises a plurality of layers,

the entire projection area of the non-existing portion of the stain-proofing layer is contained in the inner area.

4. The covering member according to any one of claims 1 to 3, wherein,

the adhesive member is in the form of a ring,

at least a part of the inner region is provided with a portion continuous in the circumferential direction of the ring and not provided with a print layer.

5. The covering member according to any one of claims 1 to 3, wherein,

the printing layer is formed in a strip shape along an end of the transparent substrate, the adhesive member contact portion projection area includes one end and the other end of the printing layer in a width direction,

The adhesive member contact portion projection region has: a portion not including the print layer is continuously formed between one end portion and the other end portion in the width direction of the print layer.

6. The covering member according to any one of claims 1 to 3, wherein,

when a region from the outer peripheral end to a portion 50 μm inward from the outer peripheral end of the second main surface is set as an outer peripheral end-near region, a portion of the inner region is included in the outer peripheral end-near region, and a portion of the inner region included in the outer peripheral end-near region is not provided with the print layer.

7. The covering member according to any one of claims 1 to 3, wherein,

the transparent substrate is a glass substrate.

8. The cover member of claim 7, wherein the cover member comprises a plurality of layers,

the glass matrix is a chemically strengthened glass matrix.

9. The covering member according to any one of claims 1 to 3, wherein,

an adhesion layer is further provided between the first main surface of the transparent substrate and the stain-proofing layer.